TWI485519B - Pattern forming method, chemically amplified resist composition, and resist film - Google Patents

Description

Pattern forming method, chemically amplified resist composition, and resist film

The present invention relates to an ultra-lithographic process or other photofabrication process suitable for use in the manufacture of very large scale integration (Super LSI) or high-capacity microchips, including organic solvents. A pattern forming method of the developer, a chemically amplified resist composition used in the pattern forming method, and a resist film. In addition, a pattern forming method using a developing solution containing an organic solvent which can be suitably used for microfabrication of an electron beam using an electron beam or extreme ultraviolet (EUV) light (wavelength: around 13 nm), the pattern forming method A chemically amplified resist composition used in the present invention, and a resist film. Further, the pattern forming method of the present invention relates to a pattern forming method which can be suitably applied to a method for producing a mask or a method for producing a mold structure for a nanoimprint, and a chemical amplification type resist used in the pattern forming method. Etchant composition, and resist film.

Conventionally, in a manufacturing process of a semiconductor device such as an integrated circuit (IC) or an LSI, fine processing is performed by a lithography method using a photoresist composition. In recent years, with the high integration of integrated circuits, it is required to form an ultrafine pattern in a submicron region or a quarter micron region. Along with this, the exposure wavelength also tends to be short-wavelength from the g-line to the i-line, and further to the KrF excimer laser light. Further, in addition to excimer laser light, lithography using electron beams or X-rays or EUV light is currently being developed.

These electron beam or X-ray or EUV photolithography methods are positioned as next-generation or next-generation pattern forming technologies, and a high-sensitivity, high-resolution resist composition is desired.

In particular, since the wafer processing time is shortened, high sensitivity is a very important issue. If high sensitivity is desired, the resolution of the limit analysis line width is lowered. Therefore, it is strongly desired to develop and satisfy these characteristics. Resist composition.

There is a trade-off between high sensitivity and high resolution. How to satisfy this high sensitivity and high resolution is very important.

The photosensitive linear or radiation-sensitive resin composition usually has a "positive type", and the exposed portion is soluble in an alkaline developing solution by exposure to radiation using a resin which is insoluble or insoluble in an alkaline developing solution. In order to form a pattern, a "negative type" is formed by using a resin which is soluble in an alkaline developing solution, and the exposed portion is hardly dissolved or insoluble in an alkaline developing solution by exposure to radiation.

As a sensitive photo-linear or radiation-sensitive resin composition suitable for the above-described lithography process using electron beam, X-ray, or EUV light, in terms of high sensitivity, it is mainly a chemical reaction using an acid catalyst. The amplified positive resist composition is studied, and a chemically amplified positive resist composition containing a phenolic resin (hereinafter referred to as a phenolic acid-decomposable resin) and an acid generator as a main component is effectively used. The above phenolic resin is insoluble or poorly soluble in an alkaline developing solution, and is soluble in an alkaline developing solution by the action of an acid.

On the other hand, when manufacturing a semiconductor element or the like, it is required to form a line, Patterns of various shapes such as grooves and holes. In order to cope with the demand for forming patterns having various shapes, not only a positive type, but also a development of a negative-type photosensitive light-sensitive or radiation-sensitive resin composition is underway, but the formation of an ultra-fine pattern is required to reduce the resolution.

In order to solve this problem, a method of developing a film obtained from an acid-decomposable resin using a developing solution other than an alkaline developing solution has been proposed (for example, see Patent Document 1).

Further, a method is known in which a film obtained from an electron beam resist containing a fullerene derivative is exposed in order to improve dry etching resistance, resolution, and sensitivity, and then an organic solvent is used. Development is performed to form a negative pattern (for example, refer to Patent Document 2 and Patent Document 3).

Other techniques for using fullerene or fullerene derivatives in a resist composition are also known in which a method of using a methanofullerene derivative having a specific structure, a photoacid generator, and The resist composition of the crosslinking agent is used to form a film, and the film is exposed to an acid crosslinking reaction, and then developed using an organic solvent to form a negative pattern (see Patent Document 4); or used in the main chain. A resist composition of a fullerene derivative is added to the cut resist composition to form a film, and after exposing the film, development is performed using an organic solvent to form a positive pattern (for example, reference) Patent Document 5).

Further, Patent Document 6 discloses that fullerene hydroxide exhibits high solubility in an ester solvent such as propylene glycol-1-monomethyl ether acetate (PGMEA), and is used for photoresist applications.

However, the current state of the art is a technology that satisfies both high sensitivity, high resolution, excellent rough properties, and excellent dry etching resistance.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2008-292975

Patent Document 2: Japanese Patent Laid-Open No. Hei 11-143074

Patent Document 3: Japanese Patent Laid-Open No. Hei 11-258796

Patent Document 4: Japanese Patent Laid-Open Publication No. 2008-513820

Patent Document 5: Japanese Patent Laid-Open Publication No. 2009-134020

Patent Document 6: Japanese Patent Laid-Open Publication No. 2010-116380

The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a pattern forming method and a chemical amplification type resistant which are excellent in not only high sensitivity, high resolution, excellent rough performance, and excellent dry etching resistance, but also excellent in development time dependency. Etchant composition, and resist film.

The present invention has the following constitution, thereby achieving the above object of the present invention.

[1] A negative pattern forming method comprising the steps of: (a) forming a film by using a chemically amplified resist composition comprising (A) having an acid-decomposable group; a fullerene derivative, (B) a compound which generates an acid by irradiation with active light or radiation, and (C) a solvent; (b) a step of exposing the film; and (c) using a developer containing an organic solvent The step to develop.

[2] The negative pattern forming method according to [1] above, wherein The total amount of the developer is from 90% by mass to 100% by mass based on the total amount of the organic solvent in the developer containing the organic solvent.

[3] The negative pattern forming method according to the above [1] or [2], wherein the content of the fullerene derivative (A) is 30% by mass based on the total solid content of the resist composition ~99% by mass.

[4] The negative pattern forming method according to any one of [1] to [3] wherein the compound (B) is produced by irradiating active light or radiation to produce the following general formula (BI) or a compound of the sulfonic acid represented by the formula (I):

In the formula (BI), Ar represents an aromatic ring, p represents an integer of 0 or more, and A represents a group having a hydrocarbon group, and when p is 2 or more, a plurality of A groups may be the same or different; [Chemical 2]

In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and R ¹ and R ² each independently represent a group selected from a hydrogen atom, a fluorine atom and an alkyl group, and a plurality of groups exist. When R ¹ and R ² may be the same or different, L represents a divalent linking group, and L may be the same or different when there are a plurality of groups, A represents a cyclic organic group, x represents an integer of 1-20, and y represents An integer from 0 to 10, and z represents an integer from 0 to 10.

[5] The negative pattern forming method according to any one of the above [1], wherein the fullerene derivative (A) has the following formula (a1) or formula (a2) Part of the structure represented:

In the formula, ALG ₁ and ALG ₂ each independently represent a group which is decomposed and desorbed by the action of an acid. When n1 is an integer of 2 or more, a plurality of ALGs ₁ may be bonded to each other, and n2 is an integer of 2 or more. In the case, a plurality of ALG ₂ may be bonded to each other; L ₁ represents a single bond or (n1+1) valent linkage with one carbon atom forming a fullerene skeleton; and L ₂ represents a carbon with a fullerene skeleton. Two bonded (n2+2) valent linking groups of atoms; X ₁ and X ₂ each independently represent -O- or -COO-; n1 and n2 each independently represent an integer of 1 to 6.

[6] The negative pattern forming method according to any one of the above [1], wherein the acid-decomposable group is protected by an alcoholic hydroxyl group by a decomposing group which is decomposed by an action of an acid. structure.

[7] The negative pattern forming method according to any one of the above [1], wherein the developing solution contains a solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent. A developer of at least one organic solvent in a group consisting of ether solvents.

[8] The negative pattern forming method according to any one of [1] to [7], further comprising (d) a step of washing using an eluent containing an organic solvent.

[9] A negative-type pattern forming method according to any one of the above [1] to [8].

[10] A chemically amplified resist composition comprising (A) a fullerene derivative having an acid-decomposable group, (B) a compound which generates an acid by irradiation with active light or radiation, and (C) a solvent And the above compound (B) is a compound which produces a sulfonic acid represented by the following formula (BI) or formula (I): [Chemical 4]

In the formula (BI), Ar represents an aromatic ring, p represents an integer of 0 or more, and A represents a group having a hydrocarbon group, and when p is 2 or more, a plurality of A groups may be the same or different;

In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R ¹ and R ² may be the same or different, L represents a divalent linking group, and L may be the same or different when there are a plurality of groups, A represents a cyclic organic group, x represents an integer of 1-20, and y represents an integer of 0-10. z represents an integer from 0 to 10.

[11] The chemically amplified resist composition according to [9] or [10] above, wherein the above fullerene derivative (A) has the following formula (a1) or formula (a2) Part of the structure represented:

In the formula, ALG ₁ and ALG ₂ each independently represent a group which is decomposed and desorbed by the action of an acid. When n1 is an integer of 2 or more, a plurality of ALGs ₁ may be bonded to each other, and n2 is an integer of 2 or more. In the case, a plurality of ALG ₂ may be bonded to each other; L ₁ represents a single bond or (n1+1) valent linkage with one carbon atom forming a fullerene skeleton; and L ₂ represents a carbon with a fullerene skeleton. Two bonded (n2+2) valent linking groups of atoms; X ₁ and X ₂ each independently represent -O- or -COO-; n1 and n2 each independently represent an integer of 1 to 6.

[12] The chemically amplified resist composition according to the above [10], wherein the acid-decomposable group is a structure in which an alcoholic hydroxyl group is protected by a decomposing group which is decomposed by an action of an acid. .

[13] A resist film formed by using the chemical amplification resist composition according to any one of [9] to [12] above.

The present invention preferably further has the following constitution.

[14] The pattern forming method according to any one of [1] to [8] above, The developer containing the organic solvent has a water content of less than 10% by mass as a whole of the developer.

[15] The pattern forming method according to any one of [1] to [8], wherein the developer is substantially free of moisture.

[16] The pattern forming method according to any one of [1] to [8] wherein the resist composition does not contain a crosslink which can crosslink the fullerene derivatives with each other by an action of an acid. Joint agent.

[17] The chemically amplified resist composition according to any one of the above [9], wherein the resist composition does not contain a fullerene derivative which can be acted upon by an acid Crosslinkers crosslinked to each other.

According to the present invention, it is possible to provide a pattern forming method, a chemically amplified resist composition, and a pattern forming method which are excellent in not only high sensitivity, high resolution, excellent rough performance, and excellent dry etching resistance, but also excellent in development time dependency, and Resist film.

Hereinafter, embodiments of the present invention will be described.

Further, in the expression of the group (atomic group) in the present specification, the unsubstituted and unsubstituted expression is not described as including not only a group having no substituent but also a group having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term "active light" or "radiation" as used in the present specification means, for example, a bright line spectrum of a mercury lamp and a far ultraviolet ray represented by an excimer laser. Extreme ultraviolet (EUV light), X-ray, electron beam, etc. Further, the term "light" as used in the present invention means active light or radiation.

In addition, the "exposure" in the present specification is not only an exposure of a far-ultraviolet light, an extreme ultraviolet ray, an X-ray, or an EUV light represented by a mercury lamp or an excimer laser, but also an electron beam, an ion beam, etc., unless otherwise specified. The drawing of the particle beam is also included in the exposure.

The pattern forming method of the present invention is a negative pattern forming method comprising the steps of: (a) forming a film using a chemically amplified resist composition, wherein the chemically amplified resist composition comprises (A) An acid-decomposable base fullerene derivative, (B) a compound which generates an acid by irradiation with active light or radiation, and (C) a solvent; (b) a step of exposing the film; and (c) use of an organic The step of developing the solvent developer.

Fullerene is generally insoluble or poorly soluble in organic solvents because of the strong interaction between the molecules of fullerene and the high density of fullerene molecules.

However, according to the pattern forming method of the present invention, by introducing an acid-decomposable group into the fullerene, the interaction between the fullerene molecules in the unexposed portion is lowered, and the density of the fullerene molecule is decreased, so that it is contained. The dissolution rate in the developer of the organic solvent increases, and the unexposed portion becomes soluble in the developer.

On the other hand, in the exposed portion, by the action of the acid generated by the exposure of the compound (B), the leaving group in the acid-decomposable group is detached from the fullerene molecule, and the interaction between the fullerene molecules is improved. Containing organic solvents The dissolution rate in the developer of the agent is drastically lowered. As a result, the exposed portion becomes insoluble or poorly soluble in the developer containing the organic solvent.

According to the above mechanism, it is presumed that the pattern forming method according to the present invention forms a negative pattern by developing using a developing solution containing an organic solvent.

However, in the microfabrication of a semiconductor element using an electron beam or EUV light, since the line width of the pattern is short, if the thickness of the resist film is not reduced, the pattern collapse is likely to occur. problem.

However, if the thickness of the resist film is reduced, there is a problem that the etching resistance is poor.

In the film of the pattern forming method of the present invention, since the fullerene skeleton of the fullerene derivative is present, the etching resistance is extremely high. Further, as described above, in the exposed portion, the presence density of the fullerene derivative is increased by the interaction between the fullerene molecules, which contributes to an improvement in etching resistance.

Therefore, in the present invention, even if the thickness of the resist film is reduced in order to suppress the problem of pattern collapse, excellent etching resistance can be obtained.

Further, since the film formation, in particular, the exposure toward the film thickness direction becomes more reliable, it is excellent in sensitivity, resolution, and roughness.

Further, the acid-decomposable group of the fullerene derivative (A) is, for example, a structure protected by an alkali-soluble group which is decomposed and decomposed by the action of an acid, and may be used by using an alkaline developer. The possibility of forming a positive pattern instead of a developing solution containing an organic solvent. However, even by acid decomposition, the fullerene derivative becomes an alkali-soluble group and is also rich. The presence of the olefinic skeleton makes it difficult to sufficiently dissolve the exposed portion in the alkaline developing solution, and thus it is difficult to obtain a pattern excellent in sensitivity, resolution, and roughness.

Further, in the case of the positive pattern forming method, in the unexposed portion, since the interaction between the fullerene molecules as described above is not improved in the present invention, the etching resistance as described in the present invention is also improved. difficult.

As described above, from the viewpoint of improvement in etching resistance, it is preferred that the resist film (in the negative pattern is an exposed portion) remaining after development, the interaction between the molecules of the fullerene derivative is made. The level is as close as possible to the level of very strong interaction between the unmodified fullerene molecules to increase the density of the fullerene derivative in the developed film.

Therefore, in the present invention, the fullerene derivative preferably has crosslinkability which is crosslinkable with other fullerene derivatives in the presence or absence of a crosslinking agent in addition to the acid-decomposable group. base. Further, the chemically amplified resist composition of the present invention preferably contains no crosslinking agent which can crosslink the fullerene derivatives with each other by the action of an acid.

The reason for this is that if the fullerene derivatives are crosslinked by a crosslinking component or the like in the exposed portion, the proximity of the fullerene skeleton is inhibited, and the density of the fullerene derivative is prevented from increasing.

In the pattern forming method of the present invention, the developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. .

The pattern forming method of the present invention preferably further comprises (d) a step of washing using an eluent containing an organic solvent.

The eluent preferably contains a solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, and an ester system. An eluent of at least one organic solvent in a group consisting of a solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

The pattern forming method of the present invention preferably includes (e) a heating step after the (b) exposure step.

The pattern forming method of the present invention may include a plurality of (b) exposure steps.

The pattern forming method of the present invention may include a plurality of (e) heating steps.

The resist film of the present invention is a film formed by using the above chemically amplified resist composition, and is, for example, a film formed by applying a resist composition on a substrate.

Hereinafter, a resist composition which can be used in the present invention will be described.

[1] (A) Fullerene derivatives having an acid-decomposable group

The so-called "fullerenes" of the fullerene derivative (hereinafter also referred to simply as the fullerene derivative (A)) used in the resist composition of the present invention means a closed shell structure. Carbon clusters. The fullerene has a carbon number of usually 60 or more and 130 or less.

Specific examples of the fullerene include C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₂ , C ₈₄ , C ₉₀ , C ₉₄ , C _{96 ,} and a highly carbon cluster having more carbon than the above. Here, the fullerene skeleton refers to a skeleton constituting the closed shell structure of the above fullerene, and generally refers to a closed shell carbon skeleton composed only of carbon atoms.

The fullerene skeleton of the fullerene derivative (A) is not limited, and among them, fullerene C ₆₀ or fullerene C _{70 is} preferable, and fullerene C _{60 is more} preferable. Fullerene C ₆₀ and fullerene C ₇₀ are obtained as main products in the production of fullerenes, and thus have an advantage of being easily obtained. That is, the fullerene derivative of the present invention is preferably a derivative of fullerene C ₆₀ or fullerene C ₇₀ , more preferably a derivative of fullerene C ₆₀ .

Further, the fullerene derivative (A) also includes, for example, a metal, a compound, or the like in the interior of the fullerene skeleton, and a compound which forms a complex with other metal atoms or compounds.

The fullerene derivative used in the resist composition of the present invention has an acid-decomposable group. More specifically, the fullerene derivative is preferably formed by providing a partial structure having an acid-decomposable group on the surface of the fullerene.

The amount of the acid-decomposable group is usually 2 or more, preferably 3 or more, more preferably 4 or more, and usually 30 or less, preferably 20 or less, and particularly preferably 10 or less.

Here, the acid-decomposable group is not particularly limited as long as it is a group which is decomposed and decomposed by the action of an acid, and it is preferred that the polar group is protected by a decomposing group which is decomposed and decomposed by the action of an acid. structure.

The polar group is not particularly limited, and examples thereof include an alcoholic hydroxyl group, a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonylamino group, and a sulfonimide. , (alkylsulfonyl) (alkylcarbonyl) methylene, (alkylsulfonyl) (alkylcarbonyl) fluorenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl醯imino, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl) fluorenylene, tris(alkylcarbonyl)methylene, tris(alkylsulfonyl) Methyl and the like.

Preferred polar groups include an alcoholic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, and more preferably an alcoholic hydroxyl group.

The fullerene derivative (A) preferably has a partial structure represented by the following formula (a1) or formula (a2) having an acid-decomposable group.

[Chemistry 7]

In the formula, ALG ₁ and ALG ₂ each independently represent a group (debonding group) which is decomposed and desorbed by the action of an acid. In the case where n1 is an integer of 2 or more, a plurality of ALGs ₁ can be combined with each other. In the case where n2 is an integer of 2 or more, a plurality of ALGs ₂ can be combined with each other.

L ₁ represents a single bond or a (n1+1)-valent linking group which is bonded to one of the carbon atoms forming the fullerene skeleton.

L ₂ represents a (n2+2)-valent linking group bonded to two of the carbon atoms forming the fullerene skeleton.

X ₁ and X ₂ each independently represent -O- or -COO-.

N1 and n2 each independently represent an integer of 1 to 6.

In the case where n1 is 1, the divalent linking group of L ₁ may be exemplified by -COO-, -OCO-, -CO-, -CS-, -O-, -S-, -SO-, -SO ₂ -, -NR-(R is a hydrogen atom or an alkyl group), an alkylene group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent aromatic ring group or The linking group in which a plurality of these groups are linked is preferably a linking group having a total carbon number of 12 or less.

In -NR-, the alkyl group represented by R may be exemplified by methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, hexyl, 2-ethylhexyl, octyl, dodecane. The alkyl group having a carbon number of 20 or less is more preferably an alkyl group having 8 or less carbon atoms, and particularly preferably an alkyl group having 3 or less carbon atoms. R is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

The alkylene group in L ₁ may be linear or branched, and examples thereof include a methylene group, an exoethyl group, a propyl group, a butyl group, a hexyl group, and a octyl group. Eight alkylene groups are preferred examples. More preferably, it is an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

The alkenyl group in L ₁ may be a group having a double bond at any position of the alkylene group described above.

The cycloalkyl group in L ₁ may be either a monocyclic or polycyclic type, and examples thereof include a cyclobutyl group, a cyclopentylene group, a cyclohexylene group, a norbornene group, and an adenantyl group ( Adamantylene), a divalent aliphatic hydrocarbon ring group having 3 to 17 carbon atoms such as diamantanylene is preferred. More preferably, it is a divalent aliphatic hydrocarbon ring group having 5 to 12 carbon atoms, and particularly preferably a divalent aliphatic hydrocarbon ring group having 6 to 10 carbon atoms.

The cycloalkenyl group in L ₁ may, for example, be a group having a double bond at any position of the above-exemplified cycloalkyl group.

The divalent nitrogen-containing non-aromatic heterocyclic group in L ₁ is preferably a non-aromatic heterocyclic group having at least one nitrogen atom and preferably from 3 to 8 members. Specifically, for example, a divalent linking group of the structure.

The divalent aromatic ring group in L ₁ may, for example, be a aryl group which may have a substituent having a carbon number of 6 to 14 such as a phenyl group, a tolyl group or a naphthyl group, or, for example, a thiophene or a furan (furan) ), pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole a divalent aromatic ring group containing a hetero ring such as thiadiazole or thiazole.

An alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkyl group, a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent aromatic ring group, and an alkane as R in -NR- in L ₁ The group may further have a substituent, and examples of such a further substituent include a hydroxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a nitro group, a cyano group, a decylamino group, and a sulfonylamino group. Methyl, ethyl, propyl, n-butyl, t-butyl, hexyl, 2-ethylhexyl, octyl and the like alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxy An alkoxy group such as a propoxy group or a butoxy group; an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; an anthracenyl group such as a methyl group, an ethyl group or a benzhydryl group; an ethoxy group or a butyl group; An oxy group such as an oxy group, a carboxyl group.

N1 is an integer of 2 or more in the case where, L (n1 + 1) Specific examples of the divalent linking group of from ₁ include divalent remove any particular embodiment disclosed above as L ₁ in the (N1-1) hydrogen atoms The group formed.

Specific examples of the (n2+2)-valent linking group in L ₂ include a group obtained by removing any n 2 hydrogen atoms from the divalent specific example disclosed as L ₁ above.

In the case where X ₁ and X ₂ are -COO-, the partial structure represented by the above formula (a1) and formula (a2) is a structure in which a carboxyl group is decomposed to generate a carboxyl group by the action of an acid. In this case, ALG ₁ and ALG ₂ are each independently preferably a group represented by -C(Rx ₁ )(Rx ₂ )(Rx ₃ ).

In the formula, Rx ₁ to Rx ₃ each independently represent a monovalent organic group.

Rx ₁ and Rx ₂ may combine to form a ring.

The monovalent organic group as Rx ₁ to Rx ₃ is preferably an alkyl group (straight chain or branched) or a cycloalkyl group (monocyclic or polycyclic).

The alkyl group of Rx ₁ to Rx ₃ is preferably a group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a t-butyl group.

The cycloalkyl group of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group having 3 to 20 carbon atoms such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclic fluorenyl group, a tetracyclododecyl group, and a diamond. A polycyclic cycloalkyl group having 4 to 20 carbon atoms such as an alkyl group.

The ring formed by the combination of Rx ₁ and Rx _{2 is} preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantyl group. More preferably, it is a monocyclic cycloalkyl group having 5 or 6 carbon atoms, and particularly preferably a cyclohexyl group.

Preferably, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ is bonded to Rx ₃ to form the above cycloalkyl group.

Rx ₁ to Rx ₃ may have a more substituent. Examples of such a substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group, and an alkoxy group. The carbonyl group (carbon number 2 to 6), the aryl group (carbon number 6 to 10), and the like are preferably 8 or less carbon atoms.

In the case where X ₁ and X ₂ are -O-, the partial structure represented by the above formula (a1) and formula (a2) is a structure in which a hydroxyl group is decomposed by the action of an acid. In this case, ALG ₁ and ALG ₂ are each independently preferably represented by a group represented by -C(Rx ₄ ) ₂ ORx ₅ and represented by -C(=O)OC(Rx ₄ ')(Rx ₅ ') ₂ a group or a group represented by -C(Rx ₆ ) ₃ .

Rx ₄ independently represents a hydrogen atom or a monovalent organic group. Rx ₄ can be combined with each other to form a ring.

Rx ₅ represents a monovalent organic group. Rx ₄ and Rx ₅ may be combined to form a ring.

Rx ₄ ' represents a hydrogen atom or a monovalent organic group.

Rx ₅ ' independently represents a monovalent organic group. Rx ₅ ' can be combined with each other to form a ring. In addition, one of Rx ₅ ' and Rx ₄ ' may be bonded to each other to form a ring.

Rx ₆ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. Two Rx ₆ can be combined with each other to form a ring. In the case where one or two of the three Rx ₆ are hydrogen atoms, at least one of the remaining Rx ₆ represents an aryl group, an alkenyl group or an alkynyl group.

Rx ₄ and Rx ₄ ' each independently represent a hydrogen atom or a monovalent organic group as described above. Rx ₄ and Rx ₄ ' are each independently preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group.

The alkyl group of Rx ₄ and Rx ₄ ' may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms. Examples of the alkyl group of Rx ₄ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group.

The cycloalkyl group of Rx ₄ and Rx ₄ ' may be a monocyclic ring or a polycyclic ring. The carbon number of the cycloalkyl group is preferably from 3 to 10, more preferably from 4 to 8. Examples of the cycloalkyl group of Rx ₄ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

Further, at least one of Rx ₄ is preferably a monovalent organic group. With such a configuration, a particularly high sensitivity can be achieved.

The alkyl group and the cycloalkyl group of Rx ₄ and Rx ₄ ' may further have a substituent. Examples of such a substituent include the same groups as those described for the substituent which may be further included in Rx ₁ to Rx ₃ .

Rx ₅ and Rx ₅ ' each independently represent a monovalent organic group as described above. Rx ₅ and Rx ₅ ' are each independently preferably an alkyl group or a cycloalkyl group, more preferably an alkyl group. The alkyl group and the cycloalkyl group may further have a substituent. Examples of such a substituent include the same groups as those described for the substituents which may be further included in the above Rx ₁ to Rx ₃ .

The alkyl group of Rx ₅ and Rx ₅ ' preferably has no substituent or has one or more aryl groups as a substituent. The unsubstituted alkyl group preferably has 1 to 20 carbon atoms. The alkyl group in the alkyl group substituted with one or more aryl groups preferably has 1 to 25 carbon atoms.

Specific examples of the alkyl group of Rx ₅ and Rx ₅ ' can be similarly exemplified as specific examples of the alkyl group of Rx ₄ and Rx ₄ '. Further, the aryl group in the alkyl group substituted with one or more aryl groups is preferably an aryl group having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group.

Further, in the case where the cycloalkyl group of Rx ₅ and Rx ₅ ' does not have a substituent, the carbon number is preferably from 3 to 20.

Specific examples of the cycloalkyl group of Rx ₅ and Rx ₅ ' can be similarly exemplified as specific examples of the cycloalkyl group of Rx ₄ and Rx ₄ '.

Rx ₆ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. Here, in the case where one or two of the three Rx ₆ are a hydrogen atom, at least one of the remaining Rx ₆ represents an aryl group, an alkenyl group or an alkynyl group. Rx _{6 is} preferably a hydrogen atom or an alkyl group.

The alkyl group, the cycloalkyl group, the aryl group, the alkenyl group, and the alkynyl group of Rx ₆ may further have a substituent, and examples of such a substituent include the substituents described in the substituents which may be further possessed by the above Rx ₁ to Rx ₃ . The same group of groups.

Examples of the alkyl group and the cycloalkyl group of Rx ₆ include the groups described for the alkyl group of Rx ₄ and Rx ₄ ' and the cycloalkyl group. Particularly, in the case where the alkyl group does not have a substituent, the carbon number is preferably from 1 to 6, more preferably from 1 to 3.

Examples of the aryl group of Rx ₆ include an aryl group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group.

The alkenyl group of Rx ₆ may, for example, be an alkenyl group having 2 to 5 carbon atoms such as a vinyl group, a propenyl group or an allyl group.

Examples of the alkynyl group of Rx ₆ include an alkynyl group having 2 to 5 carbon atoms such as an ethynyl group, a propynyl group and a butynyl group.

In the case where Rx ₄ and Rx ₅ are linked to each other to form a ring, it is preferred that one of Rx ₄ is bonded to Rx ₅ to form a ring.

A ring formed by two Rx ₄ and two Rx ₅ ' mutually, two Rx ₆ and Rx ₄ and Rx ₅ , and Rx ₅ ' and Rx ₄ ' may be connected to each other preferably with Rx ₄ and Rx ₄ described above. 'The ring in the cycloalkyl group is the same ring.

It is preferable that the acid-decomposable group is a structure which is protected by the decomposing group which is decomposed and desorbed by the action of an acid as described above. Thereby, the latitude of the development conditions can be expanded.

Here, the term "alcoholic hydroxyl group" means a hydroxyl group bonded to a hydrocarbon group, and is not limited as long as it is a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring.

The alcoholic hydroxyl group is preferably a hydroxyl group other than a hydroxyl group in an aliphatic alcohol in which an α-position carbon (a carbon atom to which a hydroxyl group is bonded) is substituted by an electron-withdrawing group (a halogen atom, a cyano group, a nitro group or the like). The hydroxyl group is preferably a primary alcoholic hydroxyl group (a group in which a carbon atom substituted by a hydroxyl group has another two hydrogen atoms different from a hydroxyl group), or a secondary group on a carbon atom substituted with a hydroxyl group which is not bonded to another electron withdrawing group. Alcoholic hydroxyl group.

In other words, the fullerene derivative (A) has a partial structure represented by the formula (a1) and a partial structure represented by the formula (a2), and is a group which generates an alcoholic hydroxyl group by the action of an acid. In the case of the group, X ₁ and X ₂ represent -O-, and the partial structure represented by the following general formula (a1-1) obtained by acid decomposition by the above partial structure and the following general formula (a2) -1) The partial structure shown is an alcoholic hydroxyl group, and L ₁ and L _{2 are selected} .

Further, as one form of the fullerene derivative having an acid-decomposable group in the present invention, the hydroxyl group of the fullerene hydroxide is protected by a decomposed group which is decomposed by the action of an acid (ie, a formula (ie, In a1), L ₁ = single bond, X ₁ = oxygen atom, n1 = 1) is also preferred.

Specific examples of the partial structure represented by the general formula (a1) are shown below, but are not limited to the specific examples.

Specific examples of the partial structure represented by the general formula (a2) are shown below, but are not limited to the specific examples.

The method for synthesizing the fullerene derivative (A) from fullerene is not particularly limited, and examples thereof include (1) etherification of fullerene as a raw material and etherification corresponding to an acid-decomposable group The agent is reacted to be etherified; (2) the fullerene hydroxide as a raw material is reacted with an esterifying agent corresponding to the acid-decomposable group to be esterified; and (3) the fullerene hydroxide as a raw material is correspondingly The acid-decomposable group-based carbonated agent is reacted to be carbonated.

The amount of the hydroxyl group in the fullerene hydroxide to be reacted is usually 2 or more, preferably 4 or more, more preferably 6 or more, and usually 46 or less, preferably 20 or less, and particularly preferably 14 or less. .

All of the hydroxyl groups of the fullerene hydroxide may be derivatized as an acid-decomposable group, or a part of the hydroxyl group may be derived as an acid-decomposable group.

In the case where a part of the hydroxyl group is derivatized as an acid-decomposable group, the "number of acid-decomposable groups: the number of hydroxyl groups" is preferably from 100:0 to 20:80, more preferably from 90:10 to 30:70. It is 80:20~40:60.

The fullerene derivative (A) may contain two or more acid-decomposable groups. According to this configuration, the reactivity and/or developability can be finely adjusted, and the optimization of the properties can be facilitated.

The fullerene derivative (A) may further have a substituent other than the acid-decomposable group. Examples of such a substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group, an alkoxycarbonyl group (carbon number 2 to 6), and an aryl group. (carbon number 6~10) and so on.

In the resist composition of the present invention, the blending ratio of the fullerene derivative (A) in the entire composition is preferably from 30% by mass to 99% by mass, more preferably from 55% by mass to 95% by mass based on the total solid content. quality%.

Further, in the present invention, the fullerene derivative (A) may be used alone or in combination of two or more. Alternatively, the fullerene derivative (A) may be used in combination with fullerene or other fullerene derivatives which do not conform to the fullerene derivative (A). In this case, in the total resin, the fullerene derivative (A) is preferably present in an amount of 50% by mass or more.

[2] A compound which produces an acid by irradiation with active light or radiation (B)

The composition of the present invention contains a compound (hereinafter also referred to as "acid generator") which generates an acid by irradiation with active light or radiation.

As the acid generator, a photoinitiator-based photoinitiator, a photoradical polymerization photoinitiator, a dye-based photodecolorizer, a photochromic agent, or a micro-resist can be appropriately selected and used. A well-known compound which produces an acid by irradiation with active light or radiation, and a mixture thereof.

For example, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imide sulfonate, an anthracene sulfonate may be mentioned. Oxime sulfonate), diazodisulfone, disulfone, o-nitrobenzyl sulfonate.

Preferred examples of the acid generator include compounds represented by the following formula (ZI), formula (ZII), and formula (ZIII).

In the above formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ has a carbon number of usually 1 to 30, preferably 1 to 20.

Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group in the ring. The group formed by the combination of two of R ₂₀₁ to R ₂₀₃ may, for example, be an alkyl group (for example, a butyl group or a pentyl group).

Z ^- represents a non-nuclear anion.

Examples of the non-nucleating anion of Z ^- include a sulfonate anion, a carboxylate anion, a sulfonimide anion, a bis(alkylsulfonyl) quinone imine, and a tris(alkylsulfonyl)methyl group. Anion, etc.

The non-nuclear anion refers to an anion having a significantly low ability to undergo a nuclear reaction, and an anion which can be decomposed over time due to a nuclear reaction in the molecule. Thereby, the stability of the resist composition with time is improved.

Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphorsulfonate anion.

Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms. For example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, decyl, decyl , undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl , cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, borneol, and the like.

Aroma of aromatic sulfonate anion and aromatic carboxylate anion The group group is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, the cycloalkyl group and the aryl group in the aliphatic sulfonate anion and the aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, the cycloalkyl group and the aryl group in the aliphatic sulfonate anion and the aromatic sulfonate anion include a nitro group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carboxyl group, and the like. a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), a cycloalkyl group (preferably having a carbon number of 3 to 15), an aryl group (preferably having a carbon number of 6 to 14), and an alkane. An oxycarbonyl group (preferably having 2 to 7 carbon atoms), a fluorenyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), and an alkylthio group (preferably, It is a carbon number of 1 to 15), an alkylsulfonyl group (preferably having a carbon number of 1 to 15), an alkylimidosulfonyl group (preferably having a carbon number of 1 to 15), and an aryloxysulfonyl group ( Preferably, the carbon number is 6 to 20), the alkylaryloxysulfonyl group (preferably having a carbon number of 7 to 20), the cycloalkylaryloxysulfonyl group (preferably having a carbon number of 10 to 20), and an alkane An oxyalkoxy group (preferably having a carbon number of 5 to 20) or a cycloalkyl alkoxy alkoxy group (preferably having a carbon number of 8 to 20). Further, examples of the aryl group and the ring structure of each group include an alkyl group (preferably having 1 to 15 carbon atoms) and a cycloalkyl group (preferably having 3 to 15 carbon atoms) as a substituent.

The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

The alkyl group, the cycloalkyl group, the aryl group and the aralkyl group in the aliphatic carboxylate anion, the aromatic carboxylate anion, and the aralkylcarboxylate anion may have a substituent. The substituent may, for example, be an aromatic sulfonate anion The substituent in the substituent is the same halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkylthio group or the like.

Examples of the sulfonium imine anion include a saccharin anion.

The alkyl group in the bis(alkylsulfonyl) quinone imine anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group. , propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, neopentyl, and the like. The substituent of the alkyl group may, for example, be a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group or a cycloalkylaryloxysulfonate. A mercapto group or the like is preferably an alkyl group substituted with a fluorine atom.

Examples of the other non-nucleating anion include phosphorus fluoride, boron fluoride, and cesium fluoride.

The non-nucleating anion of Z ^- is preferably an aliphatic sulfonate anion having at least the α position of the sulfonic acid substituted by a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group. A bis(alkylsulfonyl) quinone imine anion substituted with a fluorine atom, and a tris(alkylsulfonyl) methide anion having an alkyl group substituted with a fluorine atom. The non-nucleating anion is more preferably a perfluoroaliphatic sulfonate anion having 4 to 8 carbon atoms, a benzenesulfonate anion having a fluorine atom, more preferably a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, or a fifth Fluorobenzenesulfonate anion, 3,5-bis(trifluoromethyl)benzenesulfonate anion.

The acid generator is preferably a compound which produces a sulfonic acid represented by the following formula (BI), whereby the resolution and the rough properties are further improved. The sulfonic acid represented by the formula (BI) has an aromatic ring as a cyclic organic group. Such a ring The organic group is bulky and tends to leave the sulfonic acid generated in the exposed portion in the exposed portion as compared with the chain-based group. Therefore, it is considered that the problem that the acid is diffused in the non-exposed portion to cause an unexpected reaction can be further reduced, and the above properties can be obtained. More excellent. Further, the reason is not clear, but the development time dependency can be more excellent.

Therefore, in the case where the acid generator is, for example, a compound represented by the general formula (ZI) or the general formula (ZII), the aromatic sulfonate anion preferably produces an arylsulfonic acid represented by the following formula (BI). Anion.

In the formula (BI), Ar represents an aromatic ring, and may have a substituent in addition to the sulfonic acid group and the A group.

p represents an integer of 0 or more.

A represents a group having a hydrocarbon group.

When p is 2 or more, a plurality of A groups may be the same or different.

The general formula (BI) will be described in more detail.

The aromatic ring represented by Ar is preferably an aromatic ring having 6 to 30 carbon atoms.

Specific examples thereof include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indecene ring, and a perylene. Ring, pentacene Ring, acenaphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, Biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine (pyridazine) ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, hydrazine Phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine Ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine Phenothiazine) a ring, a phenazine ring or the like, preferably a benzene ring, a naphthalene ring or an anthracene ring, more preferably a benzene ring.

In addition to the sulfonic acid group and the A group, the substituent which the aromatic ring may have may be a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a hydroxyl group, a cyano group, a nitro group or a carboxyl group. Further, in the case of having two or more substituents, at least two substituents may be bonded to each other to form a ring.

Examples of the group having a hydrocarbon group represented by A include an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group, an aryloxy group such as a phenoxy group or a p-tolyloxy group, and a methylthio group. Alkyl thio, tert-butyl thiooxy, etc. An arylthio group such as an oxy group, a phenylthiooxy group or a p-tolylthiooxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; an ethoxy group, a methyl group, a straight-chain alkyl group and a branched alkyl group such as an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, a dodecyl group or a 2-ethylhexyl group; an alkenyl group such as a vinyl group, a propenyl group or a hexenyl group; an ethynyl group; An alkynyl group such as a propynyl group or a hexynyl group; an aryl group such as a phenyl group or a tolyl group; a fluorenyl group such as a benzamidine group, an ethenyl group or a tolyl group; and the like.

The hydrocarbon group in the hydrocarbon group-containing group represented by A may be an acyclic hydrocarbon group or a cyclic aliphatic group, and the hydrocarbon group preferably has 3 or more carbon atoms.

The A group is preferably a carbon atom which is a tertiary or tertiary carbon atom adjacent to Ar.

The acyclic hydrocarbon group in the A group may, for example, be isopropyl, tert-butyl, third pentyl, neopentyl, t-butyl, isobutyl, isohexyl, 3,3-dimethylpentyl. , 2-ethylhexyl and the like. The upper limit of the carbon number of the acyclic hydrocarbon group is preferably 12 or less, and more preferably 10 or less.

The cyclic aliphatic group in the A group may, for example, be a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group, an adamantyl group, a norbornyl group, a borneyl group or a nonenyl group ( Camphenyl), decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphoroyl, dicyclohexyl, pinenyl, etc., and may have a substituent. The upper limit of the carbon number of the cyclic aliphatic group is preferably 15 or less, and particularly preferably 12 or less.

In the case where the acyclic hydrocarbon group or the cyclic aliphatic group has a substituent, the substituent may, for example, be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a methoxy group, an ethoxy group or a third group. Alkoxy group such as butoxy group, aryloxy group such as phenoxy group or p-tolyloxy group, methylthio group, ethylthio group, An alkylthio group such as a third butyl thio group; an arylthio group such as a phenylthio group or a p-tolylthio group; an alkoxy group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; a linear alkyl group such as a carbonyl group, an ethoxy group, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, a dodecyl group or a 2-ethylhexyl group, a branched alkyl group, a cyclohexyl group or the like Alkenyl group such as alkyl group, vinyl group, propylene group or hexenyl group; alkynyl group such as ethynyl group, propynyl group or hexynyl group; aryl group such as phenyl group or tolyl group; hydroxyl group, carboxyl group, sulfonic acid group, carbonyl group and cyanogen group Base.

Specific examples of the group having a cyclic aliphatic group or an acyclic hydrocarbon group of A include the following examples.

From the viewpoint of suppressing acid diffusion, the above structure is more preferably the following structure.

p represents an integer of 0 or more, and the upper limit thereof is not particularly limited as long as it is a chemically possible number. From the viewpoint of suppressing the diffusion of acid, p usually represents 0 to 5, preferably 1 to 4, more preferably 2 to 3, and most preferably 3.

From the viewpoint of suppressing acid diffusion, the A group is preferably at least one ortho-position of the substituted sulfonic acid group, and more preferably a structure in which two ortho positions are substituted.

The acid generator of the present invention is a compound which produces an acid represented by the following formula (BII) in one aspect.

[Chemistry 19]

In the formula, A is the same as A in the formula (BI), and the two A's may be the same or different. R ₁ to R ₃ each independently represent a hydrogen atom, a group having a hydrocarbon group, a halogen atom, a hydroxyl group, a cyano group or a nitro group. Specific examples of the group having a hydrocarbon group include the same groups as those exemplified above.

The acid generator is preferably a compound which produces a sulfonic acid represented by the following formula (I). Since the sulfonic acid represented by the formula (I) has a cyclic organic group, the same analytical properties and rough properties can be obtained for the same reason as described above. Further, as described above, the reason is not clear, but the development time dependency can be further improved.

Therefore, in the case where the acid generator is, for example, a compound represented by the formula (ZI) or the formula (ZII), the aromatic sulfonate anion is preferably an anion which produces an acid represented by the following formula (I).

In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when a plurality of R ¹ and R ² are present, they may be the same or different.

L represents a divalent linking group, and when there are a plurality of L, they may be the same or different.

A represents a cyclic organic group.

x represents an integer from 1 to 20, y represents an integer from 0 to 10, and z represents an integer from 0 to 10.

The general formula (I) will be described in more detail.

The alkyl group in the alkyl group substituted by the fluorine atom of Xf is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 4. Further, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH _{2 .} CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ , wherein a fluorine atom or CF _{3 is} preferred. Particularly preferred are two Xf atoms which are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and is preferably a group having 1 to 4 carbon atoms. It is especially preferred to be a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent of R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C ₇ F _{15 .} , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ , wherein CF _{3 is} preferred.

R ¹ and R ^{2 are} preferably a fluorine atom or CF ₃ .

y is preferably 0 to 4, more preferably 0. x is preferably from 1 to 8, of which is preferred It is 1~4, especially good 1. z is preferably 0 to 8, and preferably 0 to 4.

The divalent linking group of L is not particularly limited, and examples thereof include: -COO-, -OCO-, -CONR- (R is a hydrogen atom, an alkyl group or a cycloalkyl group), -CO-, -O-, -S- Further, -SO-, -SO ₂ -, an alkylene group, a cycloalkylene group, an extended alkenyl group or a linking group in which a plurality of these groups are combined are preferably a linking group having a total carbon number of 12 or less. Preferred among these groups are -COO-, -OCO-, -CONR-, -CO-, -O-, -SO ₂ -, more preferably -COO-, -OCO-, -SO ₂ -.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and examples thereof include an alicyclic group, an aryl group, and a heterocyclic group (including not only a group having an aromatic property but also a group having no aromatic property). The group, for example, also contains a tetrahydropyran ring, a lactone ring structure, and the like.

The alicyclic group may be a single ring or a polycyclic ring, and is preferably a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group, a norbornyl group, a tricyclic fluorenyl group or a tetracyclic fluorenyl group. A polycyclic cycloalkyl group such as tetracyclododecyl or adamantyl. Among them, an alicyclic group having a large-volume structure having a carbon number of 7 or more of a norbornyl group, a tricyclic fluorenyl group, a tetracyclic fluorenyl group, a tetracyclododecyl group, and an adamantyl group can suppress post-exposure heating (Post Exposure Bake, The diffusibility in the film in the step of PEB) is preferable from the viewpoint of improvement of the Mask Error Enhancement Factor (MEEF).

The aryl group may be a single ring or a polycyclic ring, and examples thereof include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Among them, naphthalene having a low absorbance is preferable from the viewpoint of light absorbance at 193 nm.

The heterocyclic group may be a single ring or a polycyclic ring, and examples thereof include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, and a diphenyl group. And a group of a thiophene ring, a pyridine ring, and a decahydroisoquinoline ring. Among them, a group derived from a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is preferred.

Further, the cyclic organic group may also be a lactone structure.

The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be any of a straight chain and a branch, preferably a carbon number of 1 to 12), and a cycloalkyl group (which may be a single ring or more). Any of a ring and a spiro ring preferably has a carbon number of 3 to 20), an aryl group (preferably having a carbon number of 6 to 14), a hydroxyl group, an alkoxy group, an ester group, a decylamino group, and a urethane. A group, a ureido group, a thioether group, a sulfonamide group, a sulfonate group or the like. Further, the carbon constituting the cyclic organic group (the carbon contributing to the formation of the ring) may be a carbonyl carbon.

Examples of the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the following compounds (ZI-1), the compound (ZI-2), the compound (ZI-3), and the corresponding group in the compound (ZI-4). .

Further, it may be a compound having a plurality of structures represented by the general formula (ZI). R may, for example, a compound having the general formula (ZI) represented ₂₀₁ ~ R ₂₀₃ R of at least one other compound of the general formula (ZI) is represented by at least ₂₀₁ ~ R ₂₀₃ is a single bond or via a coupling A compound that binds to a structure.

Particularly preferred (ZI) components include the compounds (ZI-1), the compound (ZI-2), the compound (ZI-3), and the compound (ZI-4) described below.

The compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ of the above formula (ZI) is an aryl group, that is, a compound in which an arylsulfonium is used as a cation.

The arylsulfonium compound may be any of R ₂₀₁ to R ₂₀₃ which may be an aryl group, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group and the remainder may be an alkyl group or a cycloalkyl group.

Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an arylbicycloalkylsulfonium compound.

The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an anthracene residue, a benzofuran residue, a benzothiophene residue, and the like. When the aryl fluorene compound has two or more aryl groups, two or more aryl groups may be the same or different.

The alkyl group or cycloalkyl group which the aryl hydrazine compound has as needed is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a methyl group and an ethyl group. Propyl, n-butyl, t-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclohexyl and the like.

The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₁ to R ₂₀₃ may have an alkyl group (for example, a carbon number of 1 to 15), a cycloalkyl group (for example, a carbon number of 3 to 15), and an aryl group (for example, a carbon number of 6 to 14). An alkoxy group (for example, a carbon number of 1 to 15), a halogen atom, a hydroxyl group, or a phenylthio group is used as a substituent. Preferred substituents are a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms, more preferably carbon. An alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted on any of 3 R ₂₀₁ to R ₂₀₃ or may be substituted on all 3 of them. Further, in the case where R ₂₀₁ to R ₂₀₃ are an aryl group, the substituent is preferably substituted at the para position of the aryl group.

Next, the compound (ZI-2) will be described.

The compound (ZI-2) is a formula (ZI) R ₂₀₁ ~ R ₂₀₃ each independently represent a group of an organic compound having no aromatic ring. The term "aromatic ring" as used herein also means an aromatic ring containing a hetero atom.

The organic group containing no aromatic ring of R ₂₀₁ to R ₂₀₃ is usually a carbon number of 1 to 30, preferably a carbon number of 1 to 20.

R ₂₀₁ to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, and more preferably a linear or branched 2-sided oxyalkyl group, a 2-sided oxocycloalkyl group or an alkoxy group. A carbonylcarbonyl group, particularly preferably a linear or branched 2-sided oxyalkyl group.

The alkyl group and the cycloalkyl group of R ₂₀₁ to R ₂₀₃ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group) or carbon. A number of 3 to 10 cycloalkyl groups (cyclopentyl, cyclohexyl, norbornyl). More preferably, the alkyl group is a 2-sided oxyalkyl group or an alkoxycarbonylmethyl group. More preferably, the cycloalkyl group is a 2-sided oxocycloalkyl group.

The 2-sided oxyalkyl group may be either a straight chain or a branched group, and preferably a group having >C=O at the 2-position of the above alkyl group.

The 2-oxocycloalkyl group is preferably a group having >C=O at the 2-position of the above cycloalkyl group.

The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having a carbon number of 1 to 5 (methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group).

R ₂₀₁ to R ₂₀₃ may be further substituted by a halogen atom, an alkoxy group (for example, a carbon number of 1 to 5), a hydroxyl group, a cyano group, or a nitro group.

Next, the compound (ZI-3) will be described.

The compound (ZI-3) is a compound represented by the following formula (ZI-3) and is a compound having a benzamidine methyl phosphonium salt structure.

In the formula (ZI-3), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group or an alkylcarbonyloxy group. A cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.

R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-sided oxyalkyl group, a 2-sided oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to each other to form a ring structure, and the ring structure may also include An oxygen atom, a sulfur atom, a ketone group, an ester bond, or a guanamine bond.

Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, or a polycyclic condensed ring in which two or more of these rings are combined. The ring structure may be a 3 to 10 member ring, preferably a 4 to 8 member ring, and more preferably a 5 or 6 member ring.

Examples of the group formed by combining any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include a butyl group and a pentyl group.

The group formed by the combination of R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkyl group, and the alkyl group may, for example, be a methylene group or an exoethyl group.

Zc ^- represents a non-nucleating anion, and examples thereof include the same non-nuclear anion as Z ^- in the general formula (ZI).

The alkyl group as R _1c to R _7c may be either a straight chain or a branched group, and examples thereof include an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms. a group (for example, a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or a branched pentyl group), and examples of the cycloalkyl group include a cycloalkyl group having 3 to 10 carbon atoms ( For example, cyclopentyl, cyclohexyl).

The aryl group as R _1c to R _5c is preferably a carbon number of 5 to 15, and examples thereof include a phenyl group and a naphthyl group.

The alkoxy group as R _1c to R _5c may be any of a straight chain, a branched group, and a cyclic group, and examples thereof include an alkoxy group having 1 to 10 carbon atoms, preferably a straight chain and a branch having 1 to 5 carbon atoms. Alkoxy (for example, methoxy, ethoxy, linear or branched propoxy, linear or branched butoxy, linear or branched pentyloxy), cyclic alkoxy with 3 to 10 carbon atoms (for example, cyclopentyloxy, cyclohexyloxy).

Specific examples of R _1c ~ R _5c alkoxycarbonyl group and the alkoxy group Specific examples of the R _1c ~ R _5c alkoxy same.

Specific examples of the alkylcarbonyloxy group of R _1c to R _5c and the alkyl group of the alkylthio group are the same as the specific examples of the alkyl group as the above R _1c to R _5c .

Specific examples of the cycloalkyl group of R _1c ~ R _5c Cycloalkylcarbonyloxy in the specific examples of the R _1c ~ R _5c cycloalkyl same.

Specific examples of R _1c ~ R _5c aryloxy and arylthio and aryl group Specific examples of the R _1c ~ R _5c aryl group is the same.

Preferably, any one of R _1c to R _5c is a linear or branched alkyl group, a cycloalkyl group or a linear, branched or cyclic alkoxy group, and particularly preferably a sum of carbon numbers of R _1c to R _5c is 2~15. Thereby, the solvent solubility is further improved, and the generation of particles is suppressed during storage.

The ring structure in which any two or more of R _1c to R _5c can be bonded to each other is preferably a ring of 5 or 6 members, and particularly preferably a ring of 6 members (for example, a benzene ring).

The ring structure formed by combining R _5c and R _6c with each other may be exemplified by the combination of R _5c and R _6c to form a single bond or an alkyl group (methylene group, ethyl group, etc.) and the formula (I) A ring of 4 or more members formed by a carbonyl carbon atom and a carbon atom (excellently a ring of 5 to 6 members).

The aryl group as R _6c and R _7c is preferably a carbon number of 5 to 15, and examples thereof include a phenyl group and a naphthyl group.

The aspect of R _6c and R _7c is preferably such that both of them are alkyl groups. _Particularly , when R _6c and R _7c are each a linear or branched alkyl group having 1 to 4 carbon atoms, it is preferable that both of them are methyl groups.

Further, in R _6c and R _7c bonded together to form a ring, R _6c and R _7c binding group formed by carbon atoms is preferably an alkylene group having 2 to 10, for example, include extending ethyl, propyl stretch, Stretching butyl, stretching pentyl, stretching hexyl and the like. Further, a ring formed by combining R _6c and R _7c may have a hetero atom such as an oxygen atom in the ring.

Examples of the alkyl group and the cycloalkyl group of R _x and R _y include the same alkyl group and cycloalkyl group as those of R _1c to R _7c .

Examples of the 2-sided oxyalkyl group and the 2-sided oxocycloalkyl group of R _x and R _y include a group having a C=O group at the 2-position of the alkyl group and the cycloalkyl group as R _1c to R _7c .

Examples of the alkoxy group in the alkoxycarbonylalkyl group as R _x and R _y include the same alkoxy group as in R _1c to R _5c , and examples of the alkyl group include an alkyl group having 1 to 12 carbon atoms. It is preferably a linear alkyl group having 1 to 5 carbon atoms (for example, a methyl group or an ethyl group).

The allyl group as R _x and R _y is not particularly limited, and is preferably an unsubstituted allyl group or a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having a carbon number of 3 to 10). The allyl group substituted.

The vinyl group as R _x and R _y is not particularly limited, and is preferably an unsubstituted vinyl group or a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms). Substituted vinyl.

The ring structure formed by the combination of R _5c and R _x may be exemplified by the combination of R _5c and R _x to form a single bond or an alkyl group (methylene group, ethyl group, etc.) and the formula (I) A ring of 5 or more members formed by a sulfur atom and a carbonyl carbon atom (excellently a ring of 5 members).

Examples of the ring structure in which R _x and R _y may be bonded to each other include divalent R _x and R _y (for example, methylene, ethylidene, propyl, etc.) and the formula (ZI-3). A ring of 5 or 6 members formed by a sulfur atom together, particularly preferably a ring of 5 members (i.e., a tetrahydrothiophene ring).

R _x and R _{y are} preferably an alkyl group having 4 or more carbon atoms or a cycloalkyl group, more preferably 6 or more alkyl groups or a cycloalkyl group, and particularly preferably 8 or more alkyl groups or cycloalkyl groups.

R _1c to R _7c , R _x and R _y may have a more substituent. Examples of such a substituent include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, and a cycloalkyl group. Aryl, alkoxy, aryloxy, fluorenyl, arylcarbonyl, alkoxyalkyl, aryloxyalkyl, alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonyloxy, aryloxy A carbonyloxy group or the like.

More preferably, in the above formula (ZI-3), R _1c , R _2c , R _4c and R _5c each independently represent a hydrogen atom, and R _3c represents a group other than a hydrogen atom, that is, an alkyl group or a cycloalkyl group. Aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, halogen atom, hydroxy, nitro, alkylthio or arylthio.

The cation of the compound represented by the formula (ZI-2) or the formula (ZI-3) of the present invention is exemplified by the following specific examples.

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Next, the compound (ZI-4) will be described.

The compound (ZI-4) is represented by the following formula (ZI-4).

In the formula (ZI-4), R ₁₃ represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group or a cycloalkyl group. These groups may have a substituent.

R ₁₄ is independently represented by a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group of a cycloalkyl group. These groups may have a substituent.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R _{15 groups} may be bonded to each other to form a ring. These groups may have a substituent.

l represents an integer from 0 to 2.

r represents an integer from 0 to 8.

Z ^- represents a non-nucleating anion, and examples thereof include the same non-nucleating anion as Z ^- in the general formula (ZI).

In the formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched, preferably a group having 1 to 10 carbon atoms, preferably a methyl group or an ethyl group. N-butyl, tert-butyl, and the like.

The cycloalkyl group of R ₁₃ , R ₁₄ and R ₁₅ may, for example, be a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms), particularly preferably a cyclopropyl group or a cyclopentyl group. Cyclohexyl, cycloheptyl, cyclooctyl.

The alkoxy group of R ₁₃ and R ₁₄ is linear or branched, preferably a group having 1 to 10 carbon atoms, preferably a methoxy group, an ethoxy group, a n-propoxy group or a n-butoxy group. Wait.

The alkoxycarbonyl group of R ₁₃ and R ₁₄ is linear or branched, preferably a group having 2 to 11 carbon atoms, preferably a methoxycarbonyl group, an ethoxycarbonyl group, a n-butoxycarbonyl group or the like. .

Examples of the cycloalkyl group of R ₁₃ and R ₁₄ include a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms), and examples thereof include a monocyclic or polycyclic ring. An alkoxy group, and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. These groups may have more substituents.

The monocyclic or polycyclic cycloalkoxy group of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, and preferably has a monocyclic cycloalkyl group. The monocyclic cycloalkoxy group having a total carbon number of 7 or more means a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, and a cyclodecene group. A monocyclic cycloalkoxy group optionally having a substituent on a cycloalkoxy group such as a dialkoxy group: methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, dodecane group Alkyl group, 2-ethylhexyl group, isopropyl group, second butyl group, tert-butyl group, isopentyl group, etc., hydroxy group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, hydrazine Alkoxy group, sulfonylamino group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group, etc., alkoxy group such as methoxycarbonyl group, ethoxycarbonyl group a carbonyl group, a mercapto group such as a fluorenyl group, an ethyl fluorenyl group or a benzhydryl group; a decyloxy group such as an ethoxycarbonyl group or a butoxy group; a carboxyl group; and the like; the cycloalkyloxy group and any of the cycloalkyl groups The total number of carbon atoms in the total of the substituents is 7 or more.

Further, examples of the polycyclic cycloalkoxy group having a total carbon number of 7 or more include a norborneneoxy group, a tricyclodecyloxy group, a tetracyclodecyloxy group, and an adamantyloxy group.

The alkoxy group having a monocyclic or polycyclic cycloalkyl group for R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, and further preferably has a monocyclic ring. Alkoxy group of an alkyl group. The alkoxy group having a monocyclic cycloalkyl group having a total carbon number of 7 or more means a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group or a octyl group. Alkoxy groups such as an oxy group, a dodecyloxy group, a 2-ethylhexyloxy group, an isopropoxy group, a second butoxy group, a third butoxy group, an isopentyloxy group, etc. may have a substituent as described above. The group of the monocyclic cycloalkyl group is a group having a total carbon number of 7 or more including the substituent. For example, a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group, etc. may be mentioned, and a cyclohexylmethoxy group is preferable.

Further, examples of the alkoxy group having a polycyclic cycloalkyl group having a total carbon number of 7 or more include norbornyl methoxy group, norbornyl ethoxy group, tricyclodecyl methoxy group, tricyclodecyl ethoxy group. Base, tetracyclodecylmethoxy, tetracyclodecylethoxy, adamantylmethoxy, adamantylethoxy, etc., preferably norbornyl methoxy, norbornyl ethoxy, etc. .

The alkyl group of the alkylcarbonyl group of R ₁₄ may be the same as the above-mentioned specific example of the alkyl group as R ₁₃ to R ₁₅ .

The alkylsulfonyl group and the cycloalkylsulfonyl group of R ₁₄ are linear, branched or cyclic, preferably a group having 1 to 10 carbon atoms, and for example, a methylsulfonyl group or a methylsulfonate is preferred. Sulfhydryl, n-propylsulfonyl, n-butylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl and the like.

Examples of the substituent which each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyl group. Oxyl and the like.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, and a third group. A linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms such as an oxy group, a cyclopentyloxy group or a cyclohexyloxy group.

Examples of the above alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 2-methoxyethyl group, a 1-ethoxyethyl group, and a 2-ethoxy group. A linear, branched or cyclic alkoxyalkyl group having 2 to 21 carbon atoms such as a benzyl group.

Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, and a 1-methyl group. A linear, branched or cyclic alkoxycarbonyl group having 2 to 21 carbon atoms such as a propoxycarbonyl group, a tert-butoxycarbonyl group, a cyclopentyloxycarbonyl group or a cyclohexyloxycarbonyl group.

Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, and a n-butoxycarbonyloxy group. A linear, branched or cyclic alkoxycarbonyloxy group having 2 to 21 carbon atoms such as a tributoxycarbonyloxy group, a cyclopentyloxycarbonyloxy group or a cyclohexyloxycarbonyloxy group.

Two R ₁₅ may be bonded to each other to form a ring structure include 2 R ₁₅ in the general formula a divalent 5 together form a ring (ZI-4) sulfur atom or a 6-membered, particularly preferably a ring of 5 (ie, a tetrahydrothiophene ring), and may also be condensed with an aryl group or a cycloalkyl group. The divalent R ₁₅ may have a substituent, and examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxy group. Alkyloxy group and the like. There may be a plurality of substituents for the above ring structure, and the substituents may be bonded to each other to form a ring (aromatic or non-aromatic hydrocarbon ring, aromatic or non-aromatic heterocyclic ring, or a combination of the rings) Two or more polycyclic condensed rings, etc.).

R ₁₅ in the formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, or a divalent group in which two R ₁₅ groups are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.

The substituent which R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, or an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).

l is preferably 0 or 1, more preferably 1.

r is preferably 0 to 2.

The cation of the compound represented by the formula (ZI-4) of the present invention is exemplified by the following specific examples.

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Next, the general formula (ZII) and the general formula (ZIII) will be described.

In the general formula (ZII) and the general formula (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

The aryl group of R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, anthracene, benzofuran, benzothiophene and the like.

The alkyl group and the cycloalkyl group in R ₂₀₄ to R ₂₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group). a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).

The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of the substituent which the aryl group, the alkyl group and the cycloalkyl group of R ₂₀₄ to R ₂₀₇ have may be an alkyl group (for example, a carbon number of 1 to 15), a cycloalkyl group (for example, a carbon number of 3 to 15), or an aryl group (for example, a carbon number of 3 to 15). For example, a carbon number of 6 to 15), an alkoxy group (for example, a carbon number of 1 to 15), a halogen atom, a hydroxyl group, a phenylthio group, or the like.

Z ^- represents a non-nucleating anion, and is the same as the non-nucleating anion of Z ^- in the general formula (ZI).

Further, examples of the acid generator include compounds represented by the following formula (ZIV), formula (ZV), and formula (ZVI).

In the general formula (ZIV) to the general formula (ZVI), Ar ₃ and Ar ₄ each independently represent an aryl group.

R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkyl group, an alkenyl group or an aryl group.

Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as those of the specific examples of the aryl group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the above formula (ZI-1). Group.

Specific examples of the alkyl group and the cycloalkyl group of R ₂₀₈ , R ₂₀₉ and R ₂₁₀ include specific examples of the alkyl group and the cycloalkyl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the above formula (ZI-2). The same group is the case.

The alkyl group of A may, for example, be an alkylene group having 1 to 12 carbon atoms (for example, methylene, ethyl, propyl, isopropyl, butyl, isobutyl, etc.), The alkenyl group may, for example, be an alkenyl group having 2 to 12 carbon atoms (e.g., a vinyl group, a propenyl group, a butenyl group, etc.), and the exoaryl group of A may be a aryl group having 6 to 10 carbon atoms (for example, Stretching phenyl, stretching tolyl, stretching naphthyl, etc.).

More preferably, the acid generator is a compound represented by the formula (ZI) to the formula (ZIII).

Further, the acid generator is preferably a compound which produces an acid having one sulfonic acid group or a quinone imine group, and more preferably a compound which produces a monovalent perfluoroalkanesulfonic acid or a monovalent fluorine atom or contains a compound of an aromatic sulfonic acid substituted with a group of a fluorine atom, or a compound of a quinone acid substituted with a monovalent fluorine atom or a group containing a fluorine atom, and more preferably a fluorinated substituted alkanesulfonic acid A fluorine-substituted benzenesulfonic acid, a fluorine-substituted sulfimine or a sulfonium-substituted carbamic acid sulfonium salt. The acid generator which can be used is particularly preferably a fluorinated substituted alkanesulfonic acid, a fluorinated substituted benzenesulfonic acid or a fluorinated substituted sulfinic acid having a pKa of -1 or less, and the sensitivity is improved.

Particularly preferred examples of the acid generator are listed below.

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The acid generator can be synthesized by a known method, and can be synthesized, for example, according to the method described in JP-A-2007-161707.

The acid generator may be used alone or in combination of two or more.

Total solids of a composition that is sensitive to linear or radiation sensitive resin The content of the compound which generates an acid by irradiation with active light or radiation is preferably 0.1% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and particularly preferably 5% by mass. %~25% by mass.

[3] (C) solvent

Examples of the solvent which can be used in the preparation of the resist composition of the present invention include an alkylene glycol monoalkyl ether carboxylate, an alkylene glycol monoalkyl ether, an alkyl lactate, and an alkyl alkoxypropionate. a cyclic lactone (preferably having a carbon number of 4 to 10), a monoketone compound which may have a ring (preferably having a carbon number of 4 to 10), an alkylene carbonate, an alkyl alkoxyacetate or pyruvic acid. An organic solvent such as an alkyl ester.

Specific examples of the solvent include the solvents described in the specification of the U.S. Patent Application Publication No. 2008/0187860 [0441] to [0455].

In the present invention, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group in the structure may be used as the organic solvent.

The solvent containing a hydroxyl group and the solvent containing no hydroxyl group can be appropriately selected from the above-exemplified compounds, and the solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether, an alkyl lactate or the like, more preferably a propylene glycol monomethyl ether. , PGME, alias 1-methoxy-2-propanol), ethyl lactate. Further, the solvent containing no hydroxyl group is preferably an alkylene glycol monoalkyl ether acetate, an alkyl alkoxy propionate, a ring-containing monoketone compound, a cyclic lactone, an alkyl acetate or the like. Among these solvents, propylene glycol monomethyl ether acetate (PGMEA, alias 1-methoxy-2-ethoxypropane propane), ethyl ethoxy propionate, 2-glycol The ketone, γ-butyrolactone, cyclohexanone, and butyl acetate are preferably propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, and 2-heptanone.

The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent containing no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and particularly preferably 20/80 to 60/40. In terms of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is particularly preferable.

The solvent preferably contains propylene glycol monomethyl ether acetate, preferably propylene glycol monomethyl ether acetate alone solvent or two or more mixed solvents containing propylene glycol monomethyl ether acetate.

[4] (D) Basic compounds

In order to reduce the change in performance over time from exposure to heating, the resist composition of the present invention preferably contains (D) a basic compound.

The basic compound is preferably a compound having a structure represented by the following formula (A) to formula (E).

In the general formula (A) and the general formula (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), and a cycloalkyl group (compared Preferably, the carbon number is 3 to 20) or the aryl group (carbon number is 6 to 20), wherein R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and represent an alkyl group having 1 to 20 carbon atoms.

With respect to the above alkyl group, the alkyl group having a substituent is preferably a carbon number of 1 to 20 An aminoalkyl group, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyanoalkyl group having 1 to 20 carbon atoms.

The alkyl groups in the general formula (A) and the general formula (E) are more preferably unsubstituted.

Preferred examples of the compound include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, and alkane. Preferred examples of the aminoalkylmorpholine, piperidine, and the like include an imidazole structure, a diazabicyclo structure, a hydrazine hydroxide structure, a hydrazine carboxylate structure, and a trialkylamine structure. A compound having an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, an aniline derivative having a hydroxyl group and/or an ether bond, or the like.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like. The compound having a diazabicyclo structure may, for example, be 1,4-diazabicyclo[2,2,2]octane or 1,5-diazabicyclo[4,3,0]fluorene-5. - Alkene, 1,8-diazabicyclo[5,4,0]undec-7-ene, and the like. The compound having a ruthenium hydroxide structure may, for example, be a triarylphosphonium hydroxide, benzamidine methylphosphonium hydroxide or a ruthenium hydroxide having a 2-sided oxyalkyl group, specifically, triphenylphosphonium hydroxide or the like. (Third butylphenyl) cesium hydroxide, bis(t-butylphenyl)phosphonium hydroxide, benzamidine methyl thiophene oxime, 2-sided oxypropyl hydroxide thiophene oxime, and the like. The compound having a ruthenium carboxylate structure is a compound having an anion portion of a compound having a ruthenium hydroxide structure as a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Wait. The compound having a trialkylamine structure may, for example, be tri(n-butyl)amine or tri(n-octyl)amine. Wait. The compound having an aniline structure may, for example, be 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline or N,N-dihexylaniline. The alkylamine derivative having a hydroxyl group and/or an ether bond may, for example, be ethanolamine, diethanolamine, triethanolamine or tris(methoxyethoxyethyl)amine. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

Further preferred examples of the basic compound include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group.

The amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group preferably have at least one alkyl group bonded to a nitrogen atom. Further, it is preferred that the alkyl chain has an oxygen atom to form an oxyalkylene group. The number of the alkyloxyalkyl groups is one or more in the molecule, preferably from 3 to 9, more preferably from 4 to 6. The structure of the -oxy group alkyl group is preferably -CH ₂ CH ₂ O-, -CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-.

Specific examples of the above-mentioned amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group can be exemplified by US Patent Application Publication No. 2007/0224539 The compounds (C1-1) to (C3-3) exemplified in [0066] of the specification are not limited to these compounds.

Further, as the basic compound, a nitrogen-containing organic compound having a group which is desorbed by the action of an acid can also be used. Examples of the compound include a compound represented by the following formula (F). Further, a compound represented by the following formula (F) is desorbed by an action of an acid. Detach, showing the effective alkalinity in the system.

In the formula (F), R _a independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Further, when n = 2, two R _{a 's} may be the same or different, and two R _a may be bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having a carbon number of 20 or less) or a derivative thereof.

R _b independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. In the case of -C(R _b )(R _b )(R _b ), when one or more R _b is a hydrogen atom, at least one of the remaining R _b is a cyclopropyl group or a 1-alkoxyalkyl group.

At least two R _b may be bonded to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.

n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

In the formula (F), the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group represented by R _a and R _b may be a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group or a morpholinyl group. A functional group such as a pendant oxy group is substituted with an alkoxy group or a halogen atom.

An alkyl group, a cycloalkyl group, an aryl group or an aralkyl group of the above R (the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group may be substituted by the above functional group, alkoxy group or halogen atom), for example, List: from methane, ethane, propane, butane, pentane, a group of linear or branched alkane such as hexane, heptane, octane, decane, decane, undecane or dodecane, such as a cyclobutyl group or a cyclopentane group derived from the alkane. More than one or more than one substituted group of a cycloalkyl group such as a cyclohexyl group; from cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, rhododendron a group of a cycloalkane such as noradamantane, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methyl, from such cycloalkane groups One or more or one or more substituted groups of a linear or branched alkyl group such as a propyl group or a tributyl group; or a group derived from an aromatic compound such as benzene, naphthalene or an anthracene, derived from the aromatic compound a group such as a linear, branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl or the like More than one or more substituted groups; from pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquinoline ( a group of a heterocyclic compound such as perhydroquinoline), indazole or benzimidazole, or a group derived from the heterocyclic compound, which is a linear or branched alkyl group or a group derived from an aromatic compound. Or one or more substituted groups, and a group derived from a linear or branched alkane and a group derived from a cycloalkane may be one or more groups or groups of a group derived from an aromatic compound such as a phenyl group, a naphthyl group or a fluorenyl group. One or more substituted groups or the like, or a group in which the above substituent is substituted with a functional group such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group or a pendant oxy group.

Further, examples of the divalent heterocyclic hydrocarbon group (preferably having 1 to 20 carbon atoms) or a derivative thereof in which R _{a is} bonded to each other include a group derived from the following heterocyclic compound: pyrrolidine or piperidine. Morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-nitrogen Heterobenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-aza Anthraquinone, carbazole, benzimidazole, imidazo[1,2-a]pyridine, (1S,4S)-(+)-2,5-diaza Ring [2.2.1] heptane, 1,5,7-triazabicyclo[4.4.0]non-5-ene, anthracene, porphyrin, 1,2,3,4-tetrahydroquinoxaline a porphyrin, a perhydroquinoline, a 1,5,9-triazacyclododecane, etc.; a group derived from the heterocyclic compound as a group derived from a linear, branched alkane, derived from a cycloalkane One or more functional groups such as a group, a group derived from an aromatic compound, a group derived from a heterocyclic compound, a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, a pendant oxy group, or the like More than one substituted group, and the like.

Specific examples of the present invention include N-tert-butoxycarbonyldi-n-octylamine, N-tert-butoxycarbonyldi-n-decylamine, and N-tert-butoxycarbonyldi-n-butyl Indoleamine, N-tert-butoxycarbonyldicyclohexylamine, N-tert-butoxycarbonyl-1-adamantylamine, N-tert-butoxycarbonyl-2-adamantylamine, N- Third butoxycarbonyl-N-methyl-1-adamantylamine, (S)-(-)-1-(t-butoxycarbonyl)-2-pyrrolidinemethanol, (R)-(+ - 1 - (t-butoxycarbonyl)-2-pyrrolidinemethanol, N-tert-butoxycarbonyl-4-hydroxypiperidine, N-tert-butoxycarbonylpyrrolidine, N-third Oxycarbonylmorpholine, N-tert-butoxycarbonylpiperazine, N,N-di-t-butoxycarbonyl-1-gold Alkylamine, N,N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, N-tert-butoxycarbonyl-4,4'-diaminodiphenylmethane , N,N'-di-t-butoxycarbonylhexamethylenediamine, N,N,N'N'-tetra-butoxycarbonylhexamethylenediamine, N,N'- Di-t-butoxycarbonyl-1,7-diaminoheptane, N,N'-di-t-butoxycarbonyl-1,8-diaminooctane, N,N'-di- Third butoxycarbonyl-1,9-diaminodecane, N,N'-di-t-butoxycarbonyl-1,10-diaminodecane, N,N'-di-third Butoxycarbonyl-1,12-diaminododecane, N,N'-di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, N-tert-butoxy Carbonylbenzimidazole, N-tert-butoxycarbonyl-2-methylbenzimidazole, N-tert-butoxycarbonyl-2-phenylbenzimidazole, and the like.

The compound represented by the above formula (F) can be synthesized by a method described in JP-A-2009-199021, and JP-A-2007-298569.

The molecular weight of the basic compound is preferably from 250 to 2,000, particularly preferably from 400 to 1,000. The molecular weight of the basic compound is preferably 400 or more, more preferably 500 or more, and still more preferably 600 or more from the viewpoint of further reducing the leaf weight ratio (LWR).

These basic compounds may be used singly or in combination of two or more.

The amount of the basic compound used is usually 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass based on the solid content of the resist composition.

The ratio of use of the acid generator to the basic compound in the composition is preferably an acid generator/basic compound (mole ratio) = 2.5 to 300. That is, the sensitivity, In terms of the degree of resolution, the molar ratio is preferably 2.5 or more, and it is preferably 300 or less from the viewpoint of suppressing a decrease in resolution due to thickening of the resist pattern over time after exposure to heat treatment. . The acid generator/basic compound (mole ratio) is preferably 5.0 to 200, and particularly preferably 7.0 to 150.

[5] (E) surfactant

The resist composition of the present invention may further contain a surfactant or may not contain a surfactant, and in the case of containing a surfactant, it is more preferably a fluorine-containing and/or a lanthanoid surfactant (fluorine-based surfactant, Any one or two or more of a lanthanoid surfactant and a surfactant having both a fluorine atom and a ruthenium atom.

When the resist composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, a resist pattern having less adhesion and development defects can be provided with good sensitivity and resolution.

The surfactants described in [0276] of the specification of US Patent Application Publication No. 2008/0248425, for example, Eftop EF301, Eftop EF303 (manufactured by New Akita Chemicals Co., Ltd.), can be used for the fluorine-based and/or lanthanide-based surfactants. , Fluorad FC430, Fluorad FC431, Fluorad FC4430 (manufactured by Sumitomo 3M), Megafac F171, Megafac F173, Megafac F176, Megafac F189, Megafac F113, Megafac F110, Megafac F177, Megafac F120, Megafac R08 (DIC) ), Surflon S-382, Surflon SC101, Surflon SC102, Surflon SC103, Surflon SC104, Surflon SC105, Surflon SC106 (made by Asahi Glass), Troysol S-366 (Trow Manufactured by Troy Chemical Co., Ltd., GF-300, GF-150 (manufactured by East Asia Synthetic Chemicals Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), Eftop EF121, Eftop EF122A, Eftop EF122B, Eftop RF122C, Eftop EF125M, Eftop EF135M, Eftop EF351, Eftop EF352, Eftop EF801, Eftop EF802, Eftop EF601 (manufactured by Jemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX -204G, FTX-208G, FTX-218G, FTX-230G, FTX-204D, FTX-208D, FTX-212D, FTX-218D, FTX-222D (manufactured by Neos), and the like. Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a lanthanoid surfactant.

Further, as the surfactant, in addition to the known surfactant as shown above, a surfactant using a polymer having a fluoroaliphatic group which utilizes a telomerization reaction method (also referred to as A fluoroaliphatic compound produced by a telomer method or an oligomerization method (also referred to as an oligomer method) is derived. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

The surfactants satisfying the above may be exemplified by Megafac F178, Megafac F-470, Megafac F-473, Megafac F-475, Megafac F-476, Megafac F-472 (manufactured by DIC), having a C ₆ F ₁₃ group. a copolymer of acrylate (or methacrylate) and (poly(oxyalkylene)) acrylate (or methacrylate) having a C ₃ F ₇ -based acrylate (or methacrylate), (Poly(oxyethylene)) acrylate (or methacrylate) and (poly(oxypropylene)) acrylate (or methacrylate) copolymer.

Further, in the present invention, other surfactants other than the fluorine-based and/or lanthanoid surfactants described in [0280] of the specification of U.S. Patent Application Publication No. 2008/0248425 may be used.

These surfactants may be used singly or in combination with a plurality of surfactants.

In the case where the resist composition contains a surfactant, the amount of the surfactant used is preferably 0.0001% by mass to 2% by mass, more preferably 0.0005% by mass, based on the total amount of the resist composition (excluding the solvent). ~1% by mass.

On the other hand, when the amount of the surfactant added is 10 ppm or less with respect to the total amount of the resist composition (excluding the solvent), the surface bias of the hydrophobic resin is improved, whereby the resist film can be formed. The surface is more hydrophobic, which improves the water followability during immersion exposure.

[6] (F) cerium carboxylate

The resist composition in the present invention may contain a cerium carboxylate salt or may not contain a cerium carboxylate salt. The ruthenium carboxylate salt is exemplified by the ruthenium carboxylate salt described in the specification of the U.S. Patent Application Publication No. 2008/0187860 [0605] to [0606].

These cerium carboxylate salts can be synthesized by reacting cerium hydroxide, cerium hydroxide, ammonium hydroxide and a carboxylic acid with silver oxide in a suitable solvent.

In the case where the resist composition contains a cerium carboxylate salt, the content of the cerium carboxylate salt is usually 0.1% by mass to 20% by mass, preferably 0.5% by mass to 10% by mass based on the total solid content of the composition. More preferably, it is 1% by mass to 7% by mass.

[7] (G) increases in polarity by the action of an acid and contains an organic solvent Solubility-reducing resin in developer

The resist composition of the present invention may further contain a resin whose polarity is increased by the action of an acid and whose solubility in a developing solution containing an organic solvent is lowered.

The resin (G) is, for example, a resin described in paragraphs [0106] to [0203] of JP-A-2008-292975.

In the case where the resist composition contains the resin (G), the content of the resin (G) is usually 0.1% by mass to 40% by mass, preferably 0.5% by mass to 30% by mass based on the total solid content of the composition. More preferably, it is 1% by mass to 20% by mass.

[8] (H) Other additives

The resist composition of the present invention may further contain a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound which promotes solubility in a developing solution, as needed (for example, A phenol compound having a molecular weight of 1,000 or less, an alicyclic group having a carboxyl group, or an aliphatic compound).

Such a phenolic compound having a molecular weight of 1,000 or less can be easily obtained by, for example, a method described in Japanese Patent Laid-Open No. Hei 4-122938, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. synthesis.

Specific examples of the alicyclic group or the aliphatic compound having a carboxyl group include a carboxylic acid having a steroid structure such as cholic acid, deoxycholic acid or lithocholic acid. Derivative, adamantanecarboxylic acid derivative, adamantane dicarboxylic acid, cyclohexane carboxylate The acid, cyclohexane dicarboxylic acid and the like are not limited to these compounds.

The solid content concentration of the resist composition of the present invention is usually 1.0% by mass to 10% by mass, preferably 2.0% by mass to 5.7% by mass, and particularly preferably 2.0% by mass to 5.3% by mass. By setting the solid content concentration to the above range, the resist solution can be uniformly applied onto the substrate, and a resist pattern having more excellent line edge roughness can be formed. The reason for this is not clear, but it is considered that the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, whereby aggregation of the material in the resist solution, in particular, the photoacid generator is obtained. Inhibition, as a result, a uniform resist film can be formed.

The solid content concentration means the weight percentage of the weight of the other resist component other than the solvent with respect to the total weight of the resist composition.

[9] Pattern forming method

The negative pattern forming method of the present invention comprises at least the steps of: (a) a step of forming a film (resist film) using a chemically amplified resist composition; (b) a step of exposing the film; and (c) The step of developing using a developing solution containing an organic solvent.

The resist film is formed of the above chemically amplified resist composition of the present invention, and more specifically, is preferably formed on a substrate. In the pattern forming method of the present invention, the step of forming a film of the resist composition on the substrate, the step of exposing the film, and the developing step can be carried out by a generally known method.

Further, the present invention relates to a chemically amplified resist composition for use in the above negative pattern forming method.

It is also preferred to include a pre-heating step (Prebake, PB) after the film formation and before the exposure step.

Further, it is also preferred to include a Post Exposure Bake (PEB) after the exposure step and before the development step.

The heating temperature is preferably carried out at a temperature of from 70 ° C to 120 ° C for PB and PEB, more preferably from 80 ° C to 110 ° C.

The heating time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 180 seconds, and particularly preferably from 30 seconds to 90 seconds.

Heating can be performed by a mechanism including a normal exposure and developing machine, or by using a heating plate or the like.

The reaction of the exposed portion is promoted by baking, and the sensitivity or pattern distribution is improved.

The wavelength of the light source used in the exposure apparatus of the present invention is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, etc., preferably 250 nm or less, more preferably 220 nm. The ultra-ultraviolet light having a wavelength of 1 nm to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc., preferably KrF excimer laser, ArF excimer laser, EUV or electron beam, more preferably EUV or electron beam.

The substrate on which the film is formed in the present invention is not particularly limited, and an inorganic substrate such as ruthenium, SiN, SiO ₂ or SiN; a coated inorganic substrate such as spin-on-glass (SOG); The semiconductor manufacturing step, the manufacturing process of the circuit board such as a liquid crystal or a thermal head, and the substrate which is generally used in the lithography process of other photosensitive etching processes. Further, an organic anti-reflection film may be formed between the film and the substrate as needed.

The developer (hereinafter also referred to as an organic developer) in the step of developing using a developer containing an organic solvent can be used: a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, or an ether solvent. Equipolar solvent and hydrocarbon solvent.

Examples of the ketone solvent include 1-octanone, 2-octanone, 2-heptanone (methyl amyl ketone), 1-fluorenone, 2-fluorenone, acetone, 4-heptanone, and 1-hexanone. , 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl ketone, acetone acetone, ionone , diacetone alcohol, acetonitrile methanol, acetophenone, methyl naphthone, isophorone, propyl carbonate, and the like.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol single. Butyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, and the like.

Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, and anthracene. An alcohol such as an alcohol, or a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether or diethyl ether A glycol ether solvent such as alcohol monomethyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol.

Examples of the ether solvent include, in addition to the above glycol ether solvent, dioxane, tetrahydrofuran, and the like.

For the guanamine solvent, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphonium triamine (hexamethyl) can be used. Phosphoric triamide), 1,3-dimethyl-2-imidazolidinone, and the like.

Examples of the hydrocarbon-based solvent include an aromatic hydrocarbon solvent such as toluene or xylene, and an aliphatic hydrocarbon solvent such as pentane, hexane, octane or decane.

The above solvent may be mixed in a plurality of types, and may be used in combination with a solvent other than the above or water. In order to fully exhibit the effects of the present invention, it is preferred that the water content of the entire developing solution be less than 10% by mass, and more preferably substantially no moisture.

In other words, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and preferably 95% by mass or more and 100% by mass or less based on the total amount of the developer.

The organic developer is particularly preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

The vapor pressure of the organic developer is preferably 5 kPa or less at 20 ° C, particularly preferably 3 kPa or less, and particularly preferably 2 kPa or less. When the vapor pressure of the organic developing solution is 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, and temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is changed. Good.

Specific examples of the vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutylketone, and a ring. Ketone solvents such as ketone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethyl Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methyl An ester solvent such as oxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate or propyl lactate, n-propanol, isopropanol, n-butanol, second butanol, An alcohol solvent such as tributyl alcohol, isobutanol, n-hexanol, n-heptanol, n-octanol or n-nonanol; a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol, or ethylene glycol; Monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxy methyl butanol and other glycol ether solvents, tetrahydrofuran, etc. Ether solvent, amide-based solvent such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide or N,N-dimethylformamide, aromatic such as toluene or xylene Hydrocarbon solvent, aliphatic such as octane or decane Solvents.

Specific examples of the vapor pressure of 2 kPa or less which is a particularly preferable range include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, and diisobutylene. Ketone solvent such as ketone, cyclohexanone, methylcyclohexanone or phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol single Butyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl An ester solvent such as ethyl acetate, ethyl lactate, butyl lactate or propyl lactate, n-butanol, second butanol, third butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, An alcohol solvent such as n-nonanol, a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol, or ethylene glycol monomethyl ether or propylene glycol a glycol ether solvent such as monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol, N-methyl-2- A guanamine solvent such as pyrrolidone, N,N-dimethylacetamide or N,N-dimethylformamide, an aromatic hydrocarbon solvent such as xylene, or an aliphatic hydrocarbon such as octane or decane. Is a solvent.

An appropriate amount of a surfactant may be added to the organic developer as needed.

The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or a lanthanoid surfactant can be used. Examples of the fluorine- and/or lanthanide-based surfactants include the surfactants described in the following patent documents: JP-A-62-36663, JP-A-61-226746, and Japanese Patent Laid-Open Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Publication No. Hei 9-54432, Japanese Patent Laid-Open No. Hei 9-5988, U.S. Patent No. 5,405, 720, U.S. Patent No. 5,360,692, U.S. Patent No. 5,529,881, U.S. Patent No. 5,296,330, U.S. Patent No. The specification of No. 5,436,098, the specification of U.S. Patent No. 5,576,143, the specification of U.S. Patent No. 5,294,511, and the specification of U.S. Patent No. 5,824,451 are preferably nonionic surfactants. The nonionic surfactant is not particularly limited, and a fluorine-based surfactant or a lanthanoid surfactant is particularly preferably used.

The amount of the surfactant to be used is usually 0.001% by mass to 5% by mass, preferably 0.005% by mass to 2% by mass, based on the total amount of the developer. More preferably, it is 0.01% by mass to 0.5% by mass.

For the development method, for example, a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dipping method), and a method of developing a developing solution on the surface of the substrate by using the surface tension and standing still for a certain period of time ( a puddle method; a method of spraying a developer onto a surface of a substrate (jet method); a method of continuously ejecting a developer while scanning a developer at a constant speed on a substrate rotating at a constant speed (dynamically) "dynamic dispense method" and the like.

In the case where the above various development methods include a step of ejecting a developing solution from a developing nozzle of the developing device to the resist film, the ejection pressure of the ejected developing solution (the flow rate per unit area of the ejected developing solution) is preferably 2 mL. /sec/mm ² or less is more preferably 1.5 mL/sec/mm ² or less, and particularly preferably 1 mL/sec/mm ² or less. There is no particular lower limit of the flow rate, and in consideration of the treatment amount, it is preferably 0.2 mL/sec/mm ² or more.

By setting the discharge pressure of the developer to be discharged to the above range, pattern defects caused by the resist residue after development can be remarkably reduced.

The details of the mechanism are not determined. It is generally considered that the pressure applied to the resist film by the developer is reduced by setting the discharge pressure to the above range, and the resist film and the resist pattern are suppressed. Inadvertently removed or collapsed.

Further, the discharge pressure (mL/sec/mm ² ) of the developer is a value at the exit of the developing nozzle in the developing device.

The method of adjusting the discharge pressure of the developer may be, for example, a method of adjusting the discharge pressure by a pump or the like; or by supplying from a pressure tank. The method of adjusting the pressure and changing it.

Further, after the step of developing using a developing solution containing an organic solvent, a step of stopping the development while replacing the other solvent may be performed.

It is preferred to include a step of washing with an eluent after the step of developing using a developing solution containing an organic solvent.

The eluent used in the rinsing step after the step of developing using the developing solution containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a general solution containing an organic solvent can be used. The eluent is preferably an eluent containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, and the ether solvent include the same solvents as those described for the developer containing the organic solvent.

After the step of developing using a developing solution containing an organic solvent, it is more preferred to use a solution containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent. The step of washing with a washing liquid is preferably a step of washing with an eluent containing an alcohol solvent or an ester solvent, and particularly preferably a step of washing with a solvent containing a monohydric alcohol, preferably performing the step of washing. The step of washing with an eluent containing a monohydric alcohol having 5 or more carbon atoms.

Here, the monohydric alcohol used in the elution step may, for example, be a linear, branched or cyclic monohydric alcohol, and specifically, 1-butanol, 2-butanol, 3-methyl-1-butene may be used. Alcohol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4- Methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octyl Alcohol, 4-octanol, etc., particularly preferred monohydric alcohols having a carbon number of 5 or more may be 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol or 3-methyl- 1-butanol and the like.

A plurality of the above components may be used in combination, and may be used in combination with an organic solvent other than the above.

The water content in the eluent is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The vapor pressure of the eluent used after the step of developing using a developing solution containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa. Above, below 3kPa. By setting the vapor pressure of the eluent to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and the swelling due to the penetration of the eluent is suppressed, and the dimensional uniformity in the wafer surface is changed. Good.

An appropriate amount of surfactant can also be added to the eluent for use.

In the rinsing step, the wafer which has been developed using the developer containing the organic solvent is subjected to a cleaning treatment using the above-described eluent containing an organic solvent. The method of the cleaning treatment is not particularly limited. For example, a method of continuously ejecting the eluent on a substrate rotating at a constant speed (spin coating method) and immersing the substrate in a tank filled with the eluent must be applied. The method of time (dipping method), the method of spraying the eluent on the surface of the substrate (spraying method), etc., and preferably, the cleaning treatment is performed by a spin coating method, and after washing, The substrate is rotated at a speed of 2000 rpm to 4000 rpm to remove the eluent from the substrate. In addition, it is also preferred to include a heating step (Post Bake) after the rinsing step. The developer and the eluent remaining between the patterns and inside the pattern are removed by baking. The heating step after the rinsing step is usually carried out at 40 ° C to 160 ° C, preferably 70 ° C to 95 ° C, usually for 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

Instance

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the examples.

Synthesis Example 1: Synthesis of fullerene derivative (1)

C ₆₀ (OH) _5.2 (O-CH ₂ C(=O)O ^t Bu) _{4.8 was} produced in the same manner as in Example 1 of JP-A-2010-116380.

That is, to a suspension of 1.0 g (1.12 mmol) of fullerene (average hydroxide number 10) C ₆₀ (OH) ₁₀ in tetrahydrofuran (THF) (20 mL) and acetone (40 mL) manufactured by Frontier Carbon Co., Ltd. 8 g of potassium carbonate and 10 mL of butyl bromoacetate (68.2 mmol) were added, and the mixture was stirred at 25 ° C for 1 hour. Then, the reaction liquid was heated to 55 ° C and further stirred for 12 hours. Then, the reaction liquid was filtered through Celite (developing solution: ethyl acetate) to remove the solvent, and then ethyl acetate and water were added to carry out a liquid separation operation. The organic phase was dried over sodium sulfate, filtered, and the solution was concentrated, then crystallized from 300 mL of hexane, and vacuum dried at 50 ° C to obtain C ₆₀ (OH) _5.2 (O-CH ₂ C ( =O)OtBu) _4.8 As a brown solid (0.74 g, yield 46%) of fullerene derivative (1).

Synthesis Example 2: Synthesis of fullerene derivative (2)

To a suspension of 1.0 g (1.12 mmol) of Fullerene Carbonate fullerene (average hydroxide number 10) C ₆₀ (OH) ₁₀ in tetrahydrofuran (THF) (20 mL), acetone (40 mL), add xin 2.1 g (13.5 mmol) of vinyl ether and 2.3 mg (0.01 mmol) of camphorsulfonic acid were stirred for 24 hours. Then, the reaction liquid was filtered through Celite (developing solution: ethyl acetate) to remove the solvent, and then ethyl acetate and water were added to carry out a liquid separation operation. The organic phase was dried over sodium sulfate, filtered, and the solution was concentrated, and then crystallized from 300 mL of a mixed solvent of methanol-water (95:5), and vacuum-dried at 50 ° C, whereby C ₆₀ (OH) was obtained. ₆ (O-CH(CH ₃ )OC ₈ H ₁₇ ) ₄ as a fullerene derivative (2) as a brown solid (0.44 g, yield 26%).

<Preparation of resist composition>

The components shown in the following Table 1 were dissolved in the solvent shown in Table 1, and each of the resists of Example 1 to Example 11 and Comparative Example 1 was prepared by filtration using a polytetrafluoroethylene filter having a pore diameter of 0.1 μm. Composition.

The abbreviations in Table 1 are as follows.

PAG-1 to PAG-13: The following compounds are respectively indicated.

CA-1: represents the following resin. The repeating unit ratio, the mass average molecular weight (Mw), and the degree of dispersion (Mw/Mn) are as shown in Table 1.

N-1 to N-5: respectively represent the following compounds.

AD-1 to AD-2: The following compounds are respectively indicated.

W-1: Megafac F176 (made by DIC) (fluorine)

W-2: Megafac R08 (made by DIC) (fluorine and antimony)

W-3: Polyoxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

W-4: Troysol S-366 (manufactured by Troy Chemical Co., Ltd.)

W-5: KH-20 (made by Asahi Kasei Co., Ltd.)

W-6: PolyFox ^TM PF-6320 (manufactured by OMNOVA solution inc.) (fluorine system)

Group a

SL-1: Propylene glycol monomethyl ether acetate (PGMEA)

SL-2: Propylene glycol monomethyl ether propionate

SL-3: 2-heptanone

Group b

SL-4: ethyl lactate

SL-5: Propylene Glycol Monomethyl Ether (PGME)

SL-6: cyclohexanone

Group c

SL-7: γ-butyrolactone

SL-8: propyl carbonate

Using the prepared resist composition, a resist pattern was formed in the following manner.

Example 1

The prepared resist composition was uniformly coated on a ruthenium substrate treated with hexamethyldiazepine using a spin coater, and dried by heating on a hot plate at 110 ° C for 90 seconds to form a film. A resist film having a thickness of 100 nm.

The resist film was subjected to electron beam irradiation using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage: 50 keV). Immediately after the irradiation, heating was carried out on a hot plate at 120 ° C for 90 seconds. Further, using butyl acetate to develop at 23 ° C for 60 seconds to 4-methyl-2-pentanol After rinsing for 30 seconds, it was dried to obtain a 1:1 line and space pattern resist pattern having a line width of 100 nm.

Example 2 to Example 11, Comparative Example 1

A 1:1 line and space resist pattern having a line width of 100 nm was obtained in the same manner as in the method of Example 1 except that the resist composition described in Table 1 was used.

<Evaluation method> [Sensitivity]

The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.). The irradiation energy (Eopt) when the 1:1 line having a line width of 100 nm and the spatial pattern were analyzed was used as the sensitivity.

[resolving power]

The ultimate analytical force (the minimum line width of the line-to-space separation analysis) at the irradiation amount that exhibits the above sensitivity is used as the analytical force. The smaller the value, the better the performance.

[line edge roughness (LER)]

For any 30 points in the longitudinal direction of 50 μm of the line width 100 nm line pattern at the irradiation amount indicating the above sensitivity, a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.) was used to measure the respective points and edges. The distance between the reference lines is obtained, and the standard deviation is obtained to calculate 3σ (nm).

[Development time dependence]

The same evaluation was performed except that the development time was set to 120 seconds. The rate of change of the sensitivity (ΔEopt/Eopt) is calculated from the difference between Eopt in the development time of 60 seconds and the Eopt in the development time of 120 seconds, that is, the variation in sensitivity (ΔEopt/Eopt), and when the comparative example 1 is set to 100 The relative value is evaluated. The smaller value means that the change in sensitivity is small, the development time dependency is good, and the development process tolerance is large.

[Dry-resistant etching resistance]

The resist compositions of the examples and the comparative examples were uniformly coated on a ruthenium substrate treated with hexamethyldioxane using a spin coater, and dried by heating on a hot plate at 110 ° C for 90 seconds. A resist film having a film thickness of 100 nm was formed. The obtained resist film was subjected to total exposure using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage of 50 keV) at an exposure amount of 20 μC/cm ² , and further baked at 110 ° C for 60 seconds. Then, the resist film thickness was measured.

Then, a mixed gas of CF ₄ (10 mL/min), O ₂ (20 mL/min), and Ar (1000 mL/min) was used, and plasma etching was performed for 30 seconds at a temperature of 23 ° C. Then, the residual film amount of the resist film was measured, and the difference between the residual film amount and the resist film thickness after baking after exposure was divided by the etching time for 30 seconds, and the obtained value was defined as the etching rate. The smaller the etching rate, the better the plasma etching resistance. In Table 2, the etching speed indicates a relative value when Comparative Example 1 is set to 100.

According to Table 2, the film obtained from the resist composition of the present invention using a fullerene derivative having an acid-decomposable group is subjected to electron beam exposure, and then developed by a developing solution containing an organic solvent. Compared with the comparative example using an acid-decomposable resin instead of a fullerene derivative, it simultaneously satisfies high sensitivity, high resolution, excellent roughness, high dry etching resistance, and excellent development time dependency.

Further, in the case where the exposure by the electron beam is changed to the exposure by EUV, the resist composition of the present invention can exhibit the same excellent effect.

[Industrial availability]

According to the present invention, it is possible to provide a pattern forming method, a chemically amplified resist composition, and an anti-etching agent which not only satisfy high sensitivity, high resolution, excellent rough performance, and excellent dry etching resistance, but also have excellent development time dependency. Etch film.

In addition, the present invention has been described in detail with reference to the specific embodiments thereof. It is understood that various changes and modifications may be made without departing from the spirit and scope of the invention.

The present application is based on Japanese Patent Application No. 2010-208625, filed on Sep.

Claims (8)

A negative pattern forming method comprising: (a) a step of forming a film using a chemically amplified resist composition comprising (A) a fullerene derivative having an acid-decomposable group And (B) a compound which generates an acid by irradiation with active light or radiation, and (C) a solvent; (b) a step of exposing the film; and (c) a step of developing using a developing solution containing an organic solvent. The negative pattern forming method according to claim 1, wherein the content of the organic solvent in the developing solution containing the organic solvent is 90% by mass or more and 100% by mass or less based on the total amount of the developing solution. The negative pattern forming method according to claim 1, wherein the content of the fullerene derivative (A) is from 30% by mass to 99% by mass based on the total solid content of the resist composition. The negative pattern forming method according to claim 1, wherein the compound (B) is produced by irradiating active light or radiation to produce a sulfonic acid represented by the following formula (BI) or formula (I). compound of: In the formula (BI), Ar represents an aromatic ring, p represents an integer of 0 or more, and A represents a group having a hydrocarbon group, and when p is 2 or more, a plurality of A groups may be the same or different; In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and R ¹ and R ² each independently represent a group selected from a hydrogen atom, a fluorine atom and an alkyl group, and a plurality of groups exist. When R ¹ and R ² may be the same or different, L represents a divalent linking group, and L may be the same or different when there are a plurality of groups, A represents a cyclic organic group, x represents an integer of 1-20, and y represents An integer from 0 to 10, and z represents an integer from 0 to 10. The negative pattern forming method according to claim 1, wherein the fullerene derivative (A) has a partial structure represented by the following formula (a1) or formula (a2): In the formula, ALG ₁ and ALG ₂ each independently represent a group which is decomposed and desorbed by the action of an acid. When n1 is an integer of 2 or more, a plurality of ALGs ₁ may be bonded to each other, and n2 is an integer of 2 or more. In the case, a plurality of ALG ₂ may be bonded to each other; L ₁ represents a single bond or (n1+1) valent linkage with one carbon atom forming a fullerene skeleton; and L ₂ represents a carbon with a fullerene skeleton. Two bonded (n2+2) valent linking groups of atoms; X ₁ and X ₂ each independently represent -O- or -COO-; n1 and n2 each independently represent an integer of 1 to 6. The negative pattern forming method according to claim 1, wherein the acid-decomposable group is a structure in which an alcoholic hydroxyl group is decomposed and decomposed by an action of an acid. The negative pattern forming method according to claim 1, wherein the developer contains a group selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. A developer of at least one organic solvent. The negative pattern forming method according to claim 1, further comprising (d) a step of washing using an eluent containing an organic solvent.